Tuning Surface, Phase, and Magnetization of Superparamagnetic Magnetite by Ionic Liquids: Single-Step Microwave-Assisted Synthesis.

Achieving colloidal and chemical stability in ferrofluids by surface modification requires multiple steps, including purification, ex situ modification steps, and operation at high temperatures. In this study, a single-step microwave-assisted methodology is developed for iron oxide nanoparticle (IONP) synthesis utilizing a series of imidazolium-based ionic liquids (ILs) with chloride, bis(trifluoromethylsulfonyl)imide, and pyrrolide anions as the reaction media, thus eliminating the use of volatile organics while enabling rapid synthesis at 80 °C as well as in situ surface functionalization. The characterized surface functionality, hydrodynamic particle size, magnetization, and colloidal stability of the IONPs demonstrate a strong dependence on the IL structure, ion coordination strength, reactivity, and hydrophilicity. The IONPs present primarily a magnetite (Fe3O4) phase with superparamagnetism with the highest saturation magnetization at 81 and 73 emu/g at 10 and 300 K, respectively. Depending on the IL coating, magnetization and exchange anisotropy decrease by 20 and 2-3 emu/g (at 35 wt % IL), respectively, but still represent the highest magnetization achieved for coated IONPs by a coprecipitation method. Further, the surface-functionalized superparamagnetic magnetite nanoparticles show good dispersibility and colloidal stability in water and dimethyl sulfoxide at 0.1 mg/mL concentration over the examined 3 month period. This study reports on the intermolecular and chemical interactions between the particle surface and the ILs under synthetic conditions as they relate to the magnetic and thermal properties of the resulting IONPs that are well suited for a variety of applications, including separation and catalysis.

Room-Temperature Ferromagnetism in Epitaxial Bilayer FeSb/SrTiO3(001) Terminated with a Kagome Lattice.

Two-dimensional (2D) magnets exhibit unique physical properties for potential applications in spintronics. To date, most 2D ferromagnets are obtained by mechanical exfoliation of bulk materials with van der Waals interlayer interactions, and the synthesis of single- or few-layer 2D ferromagnets with strong interlayer coupling remains experimentally challenging. Here, we report the epitaxial growth of 2D non-van der Waals ferromagnetic bilayer FeSb on SrTiO3(001) substrates stabilized by strong coupling to the substrate, which exhibits in-plane magnetic anisotropy and a Curie temperature above 390 K. In situ low-temperature scanning tunneling microscopy/spectroscopy and density-functional theory calculations further reveal that an Fe Kagome layer terminates the bilayer FeSb. Our results open a new avenue for further exploring emergent quantum phenomena from the interplay of ferromagnetism and topology for application in spintronics.

Haldane topological spin-1 chains in a planar metal-organic framework.

Haldane topological materials contain unique antiferromagnetic chains with symmetry-protected energy gaps. Such materials have potential applications in spintronics and future quantum computers. Haldane topological solids typically consist of spin-1 chains embedded in extended three-dimensional (3D) crystal structures. Here, we demonstrate that [Ni(µ-4,4'-bipyridine)(µ-oxalate)]n (NiBO) instead adopts a two-dimensional (2D) metal-organic framework (MOF) structure of Ni2+ spin-1 chains weakly linked by 4,4'-bipyridine. NiBO exhibits Haldane topological properties with a gap between the singlet ground state and the triplet excited state. The latter is split by weak axial and rhombic anisotropies. Several experimental probes, including single-crystal X-ray diffraction, variable-temperature powder neutron diffraction (VT-PND), VT inelastic neutron scattering (VT-INS), DC susceptibility and specific heat measurements, high-field electron spin resonance, and unbiased quantum Monte Carlo simulations, provide a detailed, comprehensive characterization of NiBO. Vibrational (also known as phonon) properties of NiBO have been probed by INS and density-functional theory (DFT) calculations, indicating the absence of phonons near magnetic excitations in NiBO, suppressing spin-phonon coupling. The work here demonstrates that NiBO is indeed a rare 2D-MOF Haldane topological material.

Understanding Heterogeneities in Quantum Materials.

Quantum materials are usually heterogeneous, with structural defects, impurities, surfaces, edges, interfaces, and disorder. These heterogeneities are sometimes viewed as liabilities within conventional systems; however, their electronic and magnetic structures often define and affect the quantum phenomena such as coherence, interaction, entanglement, and topological effects in the host system. Therefore, a critical need is to understand the roles of heterogeneities in order to endow materials with new quantum functions for energy and quantum information science applications. In this article, several representative examples are reviewed on the recent progress in connecting the heterogeneities to the quantum behaviors of real materials. Specifically, three intertwined topic areas are assessed: i) Reveal the structural, electronic, magnetic, vibrational, and optical degrees of freedom of heterogeneities. ii) Understand the effect of heterogeneities on the behaviors of quantum states in host material systems. iii) Control heterogeneities for new quantum functions. This progress is achieved by establishing the atomistic-level structure-property relationships associated with heterogeneities in quantum materials. The understanding of the interactions between electronic, magnetic, photonic, and vibrational states of heterogeneities enables the design of new quantum materials, including topological matter and quantum light emitters based on heterogenous 2D materials.

Effect of Mn doping and charge transfer on LaTi1-xMnxO3.

We report the magnetic and electronic transport properties of Mn-doped LaTi1-xMnxO3(x= 0, 0.1, 0.3, 0.5) as a function of temperature and an applied magnetic field. It was found that the Mn-doped samples show a magnetic transition which is not present in the parent LaTiO3. The Mn-doped samples showed fluctuations in magnetization at low fields below their Néel transition temperature indicating electronic phase separation in the material. Increased Mn content in the sample strengthens the ferromagnetic-like moment while maintaining G-type antiferromagnetic phase by charge transfer from Mn to Ti and influencing orbital ordering of the Ti3+t2gorbitals. The results are discussed in parallel with transport and bulk magnetization measurements detailing the electronic behavior. An additional context for the mechanism is supported by first-principles density-function theory calculations.

Designing Magnetism in High Entropy Oxides.

In magnetic systems, spin and exchange disorder can provide access to quantum criticality, frustration, and spin dynamics, but broad tunability of these responses and a deeper understanding of strong limit disorder are lacking. Here, it is demonstrated that high entropy oxides present a previously unexplored route to designing materials in which the presence of strong local compositional disorder may be exploited to generate tunable magnetic behaviors-from macroscopically ordered states to frustration-driven dynamic spin interactions. Single-crystal La(Cr0.2 Mn0.2 Fe0.2 Co0.2 Ni0.2 )O3 films are used as a model system hosting a magnetic sublattice with a high degree of microstate disorder in the form of site-to-site spin and exchange type inhomogeneity. A classical Heisenberg model simplified to represent the highest probability microstates well describes how compositionally disordered systems can paradoxically host magnetic uniformity and demonstrates a path toward continuous control over ordering types and critical temperatures. Model-predicted materials are synthesized and found to possess an incipient quantum critical point when magnetic ordering types are designed to be in direct competition, this leads to highly controllable exchange bias behaviors previously accessible only in intentionally designed bilayer heterojunctions.

Domain Wall Patterning and Giant Response Functions in Ferrimagnetic Spinels.

The manipulation of mesoscale domain wall phenomena has emerged as a powerful strategy for designing ferroelectric responses in functional devices, but its full potential is not yet realized in the field of magnetism. This work shows a direct connection between magnetic response functions in mechanically strained samples of Mn3 O4 and MnV2 O4 and stripe-like patternings of the bulk magnetization which appear below known magnetostructural transitions. Building off previous magnetic force microscopy data, a small-angle neutron scattering is used to show that these patterns represent distinctive magnetic phenomena which extend throughout the bulk of two separate materials, and further are controllable via applied magnetic field and mechanical stress. These results are unambiguously connected to the anomalously large magnetoelastic and magnetodielectric response functions reported for these materials, by performing susceptibility measurements on the same crystals and directly correlating local and macroscopic data.

Identification of Mellein as a Pathogenic Substance of Botryosphaeria dothidea by UPLC-MS/MS Analysis and Phytotoxic Bioassay.

Botryosphaeria dothidea is a pathogenic fungus that can cause apple ring rot, a destructive apple disease in China. There have been reports on its molecular pathogenesis, but the pathogenic substances still remain unknown. In the present study, instrument analysis including UPLC-high-resolution mass spectrometry (HRMS) and nuclear magnetic resonance showed that B. dothidea fermentation broth contained (R)-(-)-mellein, a well-known fungal enantiomer of mellein. For further confirmation, a UPLC-MS/MS method for the determination of mellein was developed and validated. By this method, mellein was found to also exist in B. dothidea-infected apple fruits and branches with concentration ranges of 0.14-0.94 and 5.88-80.29 mg/kg, respectively. The concentration in fruits reached a peak at 48 h after pathogen inoculation, while a sustained concentration increase was achieved within 11 days for branches. Simultaneously, it was evident that there was a relation between disease spot expansion and mellein production kinetics in apple tissue. Phytotoxic bioassay showed that mellein could cause discoloration and death of apple leaves and browning in stems. Therefore, we confirmed that mellein was one of the pathogenic substances of B. dothidea. The present study provided additional data for the research on the pathogenesis of this pathogen.

Revealing the Chemical Bonding in Adatom Arrays via Machine Learning of Hyperspectral Scanning Tunneling Spectroscopy Data.

The adatom arrays on surfaces offer an ideal playground to explore the mechanisms of chemical bonding via changes in the local electronic tunneling spectra. While this information is readily available in hyperspectral scanning tunneling spectroscopy data, its analysis has been considerably impeded by a lack of suitable analytical tools. Here we develop a machine learning based workflow combining supervised feature identification in the spatial domain and unsupervised clustering in the energy domain to reveal the details of structure-dependent changes of the electronic structure in adatom arrays on the Co3Sn2S2 cleaved surface. This approach, in combination with first-principles calculations, provides insight for using artificial neural networks to detect adatoms and classifies each based on their local neighborhood comprised of other adatoms. These structurally classified adatoms are further spectrally deconvolved. The unexpected inhomogeneity of electronic structures among adatoms in similar configurations is unveiled using this method, suggesting there is not a single atomic species of adatoms, but rather multiple types of adatoms on the Co3Sn2S2 surface. This is further supported by a slight contrast difference in the images (or slight size variation) of the topography of the adatoms.

Bayesian Learning of Adatom Interactions from Atomically Resolved Imaging Data.

Atomic structures and adatom geometries of surfaces encode information about the thermodynamics and kinetics of the processes that lead to their formation, and which can be captured by a generative physical model. Here we develop a workflow based on a machine-learning-based analysis of scanning tunneling microscopy images to reconstruct the atomic and adatom positions, and a Bayesian optimization procedure to minimize statistical distance between the chosen physical models and experimental observations. We optimize the parameters of a 2- and 3-parameter Ising model describing surface ordering and use the derived generative model to make predictions across the parameter space. For concentration dependence, we compare the predicted morphologies at different adatom concentrations with the dissimilar regions on the sample surfaces that serendipitously had different adatom concentrations. The proposed workflow can be used to reconstruct the thermodynamic models and associated uncertainties from the experimental observations of materials microstructures. The code used in the manuscript is available at https://github.com/saimani5/Adatom_interactions.

Magnetic and dielectric property control in the multivalent nanoscale perovskite Eu0.5Ba0.5TiO3.

We report nanoscale Eu0.5Ba0.5TiO3, a multiferroic in the bulk and candidate in the search to quantify the electric dipole moment of the electron. Eu0.5Ba0.5TiO3, in the form of nanoparticles and other nanostructures is interesting for nanocomposite integration, biomedical imaging and fundamental research, based upon the prospect of polarizability, f-orbital magnetism and tunable optical/radio luminescence. We developed a [non-hydrolytic]sol-[H2O-activated]gel route, derived from in-house metallic Ba(s)/Eu(s) alkoxide precursors and Ti{(OCH(CH3)2}4. Two distinct nanoscale compounds of Ba:Ti:Eu with the parent perovskite crystal structure were produced, with variable dielectric, magnetic and optical properties, based on altering the oxidizing/reducing conditions. Eu0.5Ba0.5TiO3 prepared under air/O2 atmospheres produced a spherical core-shell nanostructure (30-35 nm), with perovskite Eu0.5Ba0.5TiO3 nanocrystal core-insulating oxide shell layer (∼3 nm), presumed a pre-pyrochlore layer abundant with Eu3+. Fluorescence spectroscopy shows a high intensity 5D0→7F2 transition at 622 nm and strong red fluorescence. The core/shell structure demonstrated excellent capacitive properties: assembly into dielectric thin films gave low conductivity (2133 GΩ mm-1) and an extremely stable, low loss permittivity of εeff∼25 over a wide frequency range (tan δ < 0.01, 100 kHz-2 MHz). Eu0.5Ba0.5TiO3 prepared under H2/argon produced more irregular shaped nanocrystals (20-25) nm, with a thin film permittivity around 4 times greater (εeff 101, tan δ < 0.05, 10 kHz-2 MHz, σ∼59.54 kΩ mm-1). Field-cooled magnetization values of 0.025 emu g-1 for EBTO-Air and 0.84 emu g-1 for EBTO-Argon were observed. X-ray photoelectron spectroscopy analysis reveals a complex interplay of EuII/III/TiIII/IV configurations which contribute to the observed ferroic and fluorescence behavior.

Nanoscale Superconducting States in the Fe-Based Filamentary Superconductor of Pr-Doped CaFe2As2.

The low-temperature scanning tunneling microscope and spectroscopy (STM/STS) are used to visualize superconducting states in the cleaved single crystal of 9% praseodymium-doped CaFe2As2 (Pr-Ca122) with Tc ≈ 30 K. The spectroscopy shows strong spatial variations in the density of states (DOS), and the superconducting map constructed from spectroscopy discloses a localized superconducting phase, as small as a single unit cell. The comparison of the spectra taken at 4.2 K and 22 K (below vs. close to the bulk superconducting transition temperature) from the exact same area confirms the superconducting behavior. Nanoscale superconducting states have been found near Pr dopants, which can be identified using dI/dV conductance maps at +300 mV. There is no correlation of the local superconductivity to the surface reconstruction domain and surface defects, which reflects its intrinsic bulk behavior. We, therefore, suggest that the local strain of Pr dopants is competing with defects induced local magnetic moments; this competition is responsible for the local superconducting states observed in this Fe-based filamentary superconductor.

Magnetic Texture in Insulating Single Crystal High Entropy Oxide Spinel Films.

Magnetic insulators are important materials for a range of next-generation memory and spintronic applications. Structural constraints in this class of devices generally require a clean heterointerface that allows effective magnetic coupling between the insulating layer and the conducting layer. However, there are relatively few examples of magnetic insulators that can be synthesized with surface qualities that would allow these smooth interfaces and precisely tuned interfacial magnetic exchange coupling, which might be applicable at room temperature. In this work, we demonstrate an example of how the configurational complexity in the magnetic insulator layer can be used to realize these properties. The entropy-assisted synthesis is used to create single-crystal (Mg0.2Ni0.2Fe0.2Co0.2Cu0.2)Fe2O4 films on substrates spanning a range of strain states. These films show smooth surfaces, high resistivity, and strong magnetic responses at room temperature. Local and global magnetic measurements further demonstrate how strain can be used to manipulate the magnetic texture and anisotropy. These findings provide insight into how precise magnetic responses can be designed using compositionally complex materials that may find application in next-generation magnetic devices.

Superconductivity with T c ≈ 7 K under pressure for Cu- and Au-doped BaFe2As2.

It is noteworthy that chemical substitution of BaFe2As2 (122) with the noble elements Cu and Au gives superconductivity with a maximum T c ≈ 3 K, while Ag substitution (Ag-122) stays antiferromagnetic. For Ba(Fe1-x TM x )2As2, TM = Cu, Au, or Ag, and by doping an amount of x = 0.04, a-lattice parameter slightly increases (0.4%) for all TM dopants, while c-lattice decreases (-0.2%) for TM = Cu, barely moves (0.05%) for Au, and increases (0.2%) for Ag. Despite the naive expectation that the noble elements of group 11 should affect the quantum properties of 122 similarly, they produce significant differences extending to the character of the ground state. For the Ag-122 crystal, evidence of only a filamentary superconductivity is noted with pressure. However, for Au and Cu doping (x ≈ 0.03) we find a substantial improvement in the superconductivity, with T c increasing to 7 K and 7.5 K, respectively, under 20 kbar of pressure. As with the ambient pressure results, the identity of the dopant therefore has a substantial impact on the ground state properties. Density functional theory calculations corroborate these results and find evidence of strong electronic scattering for Au and Ag dopants, while Cu is comparatively less disruptive to the 122 electronic structure.

Two-Dimensional Palladium Diselenide with Strong In-Plane Optical Anisotropy and High Mobility Grown by Chemical Vapor Deposition.

Two-dimensional (2D) palladium diselenide (PdSe2 ) has strong interlayer coupling and a puckered pentagonal structure, leading to remarkable layer-dependent electronic structures and highly anisotropic in-plane optical and electronic properties. However, the lack of high-quality, 2D PdSe2 crystals grown by bottom-up approaches limits the study of their exotic properties and practical applications. In this work, chemical vapor deposition growth of highly crystalline few-layer (≥2 layers) PdSe2 crystals on various substrates is reported. The high quality of the PdSe2 crystals is confirmed by low-frequency Raman spectroscopy, scanning transmission electron microscopy, and electrical characterization. In addition, strong in-plane optical anisotropy is demonstrated via polarized Raman spectroscopy and second-harmonic generation maps of the PdSe2 flakes. A theoretical model based on kinetic Wulff construction theory and density functional theory calculations is developed and described the observed evolution of "square-like" shaped PdSe2 crystals into rhombus due to the higher nucleation barriers for stable attachment on the (1,1) and (1,-1) edges, which results in their slower growth rates. Few-layer PdSe2 field-effect transistors reveal tunable ambipolar charge carrier conduction with an electron mobility up to ≈294 cm2 V-1 s-1 , which is comparable to that of exfoliated PdSe2 , indicating the promise of this anisotropic 2D material for electronics.

Atomically thin half-van der Waals metals enabled by confinement heteroepitaxy.

Atomically thin two-dimensional (2D) metals may be key ingredients in next-generation quantum and optoelectronic devices. However, 2D metals must be stabilized against environmental degradation and integrated into heterostructure devices at the wafer scale. The high-energy interface between silicon carbide and epitaxial graphene provides an intriguing framework for stabilizing a diverse range of 2D metals. Here we demonstrate large-area, environmentally stable, single-crystal 2D gallium, indium and tin that are stabilized at the interface of epitaxial graphene and silicon carbide. The 2D metals are covalently bonded to SiC below but present a non-bonded interface to the graphene overlayer; that is, they are 'half van der Waals' metals with strong internal gradients in bonding character. These non-centrosymmetric 2D metals offer compelling opportunities for superconducting devices, topological phenomena and advanced optoelectronic properties. For example, the reported 2D Ga is a superconductor that combines six strongly coupled Ga-derived electron pockets with a large nearly free-electron Fermi surface that closely approaches the Dirac points of the graphene overlayer.

Defects in Highly Anisotropic Transition-Metal Dichalcogenide PdSe2.

The atomic and electronic structures of pristine PdSe2 as well as various intrinsic vacancy defects in PdSe2 are studied comprehensively by combining scanning tunneling microscopy, spectroscopy, and density functional theory calculations. Other than the topmost Se atoms, sublayer Pd atoms and the intrinsic Pd and Se vacancy defects are identified. Both VSe and VPd defects induce defect states near the Fermi level. As a result, the vacancy defects can be negatively charged by a tip gating effect. At negative sample bias, the screened Coulomb interaction between the scanning tunneling microscopy (STM) tip and the charged vacancies creates a disk-like protrusion around the VPd and crater-like features around VSe. The magnification effect of the long-range charge localization at the charged defect site makes sublayer defects as deep as 1 nm visible even in STM images. This result proves that by gating the probe, scanning probe microscopy can be used as an easy tool for characterizing sublayer defects in a nondestructive way.

Lattice disorder effect on magnetic ordering of iron arsenides.

This study investigates magnetic ordering temperature in nano- and mesoscale structural features in an iron arsenide. Although magnetic ground states in quantum materials can be theoretically predicted from known crystal structures and chemical compositions, the ordering temperature is harder to pinpoint due to potential local lattice variations that calculations may not account for. In this work we find surprisingly that a locally disordered material can exhibit a significantly larger Néel temperature (TN) than an ordered material of precisely the same chemical stoichiometry. Here, a EuFe2As2 crystal, which is a '122' parent of iron arsenide superconductors, is found through synthesis to have ordering below TN = 195 K (for the locally disordered crystal) or TN = 175 K (for the ordered crystal). In the higher TN crystals, there are shorter planar Fe-Fe bonds [2.7692(2) Å vs. 2.7745(3) Å], a randomized in-plane defect structure, and diffuse scattering along the [00 L] crystallographic direction that manifests as a rather broad specific heat peak. For the lower TN crystals, the a-lattice parameter is larger and the in-plane microscopic structure shows defect ordering along the antiphase boundaries, giving a larger TN and a higher superconducting temperature (Tc) upon the application of pressure. First-principles calculations find a strong interaction between c-axis strain and interlayer magnetic coupling, but little impact of planar strain on the magnetic order. Neutron single-crystal diffraction shows that the low-temperature magnetic phase transition due to localized Eu moments is not lattice or disorder sensitive, unlike the higher-temperature Fe sublattice ordering. This study demonstrates a higher magnetic ordering point arising from local disorder in 122.